Ultraviolet protection of photographic-materials

ABSTRACT

A FINISHED PHOTOGRAPHIC ELEMENT, HAVING A SUPPORT AND, THEREON A PLURALITY OF DEVELOPED AND FIXED PHOTOGRAPHIC EMULSION LAYERS CONTAINING DEVELOPED DYE IMAGES AT LEAST ONE OF SAID DYE IMAGES BEING SUBJECT TO FADING BY THE ACTION OF ULTRAVIOLET RADIATION, THE EMULSION LAYER CONTAINING THE DEVELOPED DYE IMAGES SUBJECT TO FADING LYING BETWEEN THE SUPPORT AND A GELATIN LAYER CONTAINING AN ULTRAVIOLET ABSORBING HYDROPHOBIC COMPOUND REPRESENTED BY THE FOLLOWING FORMULA:   2-(2-HO,R1,R2-PHENYL),R-2,3-DIHYDRO-1H-NAPHTHO(1,2-D)-   TRIAZOLE WHERE N1 AND N3 ARE JOINED   WHEREIN R, R1 AND R2 CAN BE HYDROGEN OR AN ALKYL GROUP OF 1 TO 20 CARBON ATOMS WITH AT LEAST ONE OF THE GROUPS HAVING AT LEAST 3 CARBON ATOMS.

- nited States Patent Cfice 3,692,525 Patented Sept. 19, 1972 3,692,525ULTRAVIOLET PROTECTION OF PHOTOGRAPHIC-MATERIALS James J. Hartigan andRobert J. Clementi, Binghamton,

N.Y., assignors to General Aniline & Film Corporation,

New York, N.Y.

No Drawing. Continuation of application Ser. No. 676,731, Oct. 20, 1967.This application May 14, 1971, Ser. No. 143,619

Int. Cl. G030. 1/84 US. Cl. 96-84 R 8 Claims AnsTRAcr F Tun nlscLosunn IR N HO R wherein R, R and R can be hydrogen or an alkyl group of l to 20carbon atoms with at least one of the groups having at least 3 carbonatoms.

This is a continuation of application Ser. No. 676,731, filed Oct. 20,1967, now abandoned.

This invention relates to a photographic element, and the preparatoryprocess therefor, containing a light-sensitive silver halide emulsionstabilized against the deleterious effects of ultraviolet radiation and,more particular- 1y, to said element stabilized by the incorporationtherein of certain naphthotriazoles.

Photographic layers and, in particular, color photographic elements as aresult of their sensitization to radiation of longer wave length, areadversely effected by ultraviolet radiation. This deleterious effectalso occurs with developed color negatives and prints as a result of theattack on certain chemical species often present in the emulsion layerafter development.

Many and varied compounds have been used as ultraviolet absorbers.Criteria for acceptable absorbers include non-diifusibility, freedomfrom color, inertness, compatibility and, of course, good ultravioletabsorption and stability to ultraviolet. Such compounds have been usedeither incorporated into the silver halide emulsion layer or in a layersuperior but contiguous thereto. Among the methods for accomplishingsuch incorporation is a solvent-dispersion technique in which theultraviolet absorber compound is dissolved in an organic plasticizerwhich is, in turn, intimately blended into an aqueous gelatin solution.This procedure, however, has certain shortcomings, chief among which isa decrease in the light stability of the incorporated absorbercompounds.

It is an object of this invention, therefore to provide compoundsaffording suitable ultraviolet absorption.

It is a further object of this invention to provide such compoundscapable of incorporation into the various components or layers oflight-sensitive photographic elements without any loss in theirabsorption capacity.

In accordance with this invention it has been found that certainnaphthotriazole compounds and, in particular, certain hydroxysubstituted phenyl naphthotriazoles have superior ultraviolet absorptioncapacity which is not mitigated by incorporation into emulsions.

Therefore, this invention is based at least in part on the discoverythat naphthotriazole compounds having the structure as set forth in thegeneral formula:

not only have higher ultraviolet extinction coefiicients than compoundspreviously used for this purpose but also provide ultraviolet protectionequal or superior to the aforesaid compounds.

In the above structure, R, R and R each preferably represents hydrogenor an alkyl of 1 to 20 carbon atoms, at least one of the groups R, R andR containing at least mism of less than 250 A. may also be present.These insaid groups being 3 to 24 and preferably being 4 to 16. Othernon-chromophoric substituents with a bathochromism of less than 250A.may also be present. These include halogen, preferably chlorine,carboxy, carbalkoxy, cyan, sulfamyl (sulfonamide), carbanyl(carboxamido), etc. Substituted alkyls may also be used as, for example,hydroalkyl, haloalkyl, cyanalkyl, alkoxyalkyl and lactam methylene.Details as to specific substituents can be found in the co-pendingapplication of Catino and Strobel, Ser. No. 504,206, filed Oct. 23,1965, now abandoned, and in corresponding French Pat. 1,497,191 issuedAug. 28, 1967.

The general method of preparation of these compounds involved thediazotizing and coupling of an orthoamino phenol to an amino naphthaleneor the diazotizing and coupling of an o-nitronaphthylaminc to asubstituted phenol in such a manner that the coupling is either ortho tothe amino group of the naphtho ring or ortho to the hydroxy group of thephenol. Details as to this preparatory procedure can be found in theaforesaid 'U.S. application of Catino and Strobel and the correspondingFrench patent.

The preferred compositions of this invention include: 2(2-hydroxy-5-t-octylphenyl)naphtho(1,2-d)triazole,

N CsHrI 3 r 1 hydroxy-'-ditertiaryamyl phenyl)naphtho(1,2-d)

2 (2' hydroxy-3',5'-ditertiarybutylphenyDnaphtho(1,2 d)triazoleCharacterizing the hydroxyphenyl naphthotriazoles by the generalformula:

wherein A represents a naphthalene ring bound by 2 adjacent carbon atomsto two nitrogen atoms of the triazole ring and B represents the phenylradical containing a hydroxyl group ortho to the nitrogen atom of thetriazole ring to which the phenyl radical is linked,.the col-. umnsbelow list other substituents suitable for the compositions of thisinvention.

2N 1' I 4 Y Naphtho (2-hydroxy-5-N,N-diethylsuliamyl)phenyl.

Do (2-hydroxy-5-methyl)phenyl. Do(2-hydroxy-5-N-morpholinosulfamyl)phenyl.

p any Do (2-hydroxy-S-N,N-hydroxyethylsnllamyl)- phenyl. I Do(2-hydroxy-3 ,5 -dimethyl) phenyl. Do A (2-hydroxy-5-carbethoxy)phenyl.Do (2 -hydroxy-3 ,5 -dichloro) phenyl D o (2-hydroxy-5-N-methylsulfamyl)phenyl. Do (2-hydroxy-5-cyano) ph enyl. Do (2-hydroxy-5-carbamyl) phenyl. Do (2-hydroxy-5'-ethy1sultonyl) phenyl. Do (2'-hydroxy-5-earbobutoxy) phenyl. D o (2-hydroxy5'-N,N-dimethylcarbamyl) phenyl. Do(2-hydroxy-3,6-diethyl)phenyl. Do (2-hydroxy-5-N,N-dipro ylsulfamyl)phenyl. Do. (2-hydroxy-4,6-dibromo ph enyl. Do- (2 -hydroxy-4 -methyl)phenyl. Do (2-hydroxy-5,6-dimethyl)phenyl D(2-hydroxy-EV-chloro-fihromo) ph enyl.

famyl naphtho. G-N ,N-dimethylsul-(2-hydroxy-3,5'-ditertiaryamyl)phenyliamyl naphtha. E-cyano naphtho(2'-hydroxy-3 ,5 -ditertiaryamyl)phenyl. fi-methoxy naphtho(2"hydroxy-3,5-ditertiaryamyl)aphenyl.

E-aeetamido naphtho. I (2-hydroxy-3,5-ditertiaryamyl)phenyl.5-carbomethoxy (2-hydroxy-3,5-ditertiaryamyl)phenyl.

TABLE-C0ntinued Naphto (2-hydr oxy-3-N-methylene[2-methyl5-pyrrohdoneDphenyl. D0 (2-i1ydr 1)xy-3-N-methylene-[6-valero1actam1) pleny Do (2-ll 11ydr11)xy-3-N-methylene-[e-caprolactaml)- p eny(2i-h3trdrol3ryf Nimethylene-[fi-methyl-e-caproac am p any D0-..(2Ehyd1g] :yfl3-N1- ethylene-[Z-pmpyl piperionep eny Do(2-hyrhgorily-y-fLmethylene-[2-imldazolidinone p eny Do(2f-hydroxy;8-N-methylene-[4-methyl-2- mndaohdmoneDphenyl. Do(2f-hydroxy4;-N-methylene-[1-0yelohexyl-2 1m1dazol1d1none])phenyl. Do(2'-lfiydr xy-3-N-methylene-[3-morph0111101161) p eny I Do(Zfihydragxyy?-Ni-methylene-[2-butyl-3-m0rphonone p eny. W i Do (2-hyd]o2}ry-3 fLmethylene-[Z-thiazohchnone p eny D0- (2-l}11ydr 1 xy-3-N-methylene-[succimm1de])- p eny Do -J. (2hydroxygfiQgnethylene-B,2-dimethy1 succmlml e p eny. D0.(2-lfiydr(1)xy-3-N-methylene glutarimlde)- p eny. Do(2-hg(agony-3-I-methylene-[Z-cyanoglutanm1 e pieny Do(2'-hydroxy-3-N-methylene adipi mlde)phenyl. Do(2'41ydroxy-3-N-methy1ene[2,2-d1phenyladipimideDphenyl.

The compounds are incorporated into the emulsion layer or into a layercontiguous therewith by the solvent dispersion procedure as discussedpreviously. A representative system uses high-boiling, water-immiscibleorganic plasticizers. The plasticizer system containing the ultravioletabsorber, and such additives as desired or required, is dispersed in anaqueous gelatin solution with the aid of an emulsifier to produce afinely divided, non-crystalline form of a non-diffusable ultravioletabsorber.

Satisfactory results are obtained when these absorber compounds are usedin the concentration range of 20 to 150 milligrams per square foot ofapplied gelatin layer with the preferred concentration range being 25 to65 milligrams per square foot where the lower value is preferred for theintimately admixed gelatin-absorber-color former layer and the uppervalue is preferred for the gelatinabsorber layer superposed on thephotographic element to 'be protected. The actual concentration ofultraviolet absorber is dependent, of course, on the specific chemicalcompound to be protected and the severity of the ultraviolet exposure ofsaid compound. Color formers, asidescribed in US. Pat. 3,092,495, arecompounds capable of yielding, upon reaction with the oxidation productsof a primary amino development agent, a dye image in a colorcomplementary to the sensitivity of the layer in which it wasincorporated.

Several examples are set forth below to illustrate the nature of theinvention and the manner of carrying it out. However, the inventionshould not be considered as being limited to the details thereof.

EXAMPLE-S 1-7 minutes with a high speed mixer. The dispersion was thenchilled and noodled.

' The gelatin layers were prepared by adding 15 grams of the aboveabsorber dispersion (containing 1.2 grams of the ultraviolet absorber)to 200 ml. of a 2.5% gelatin solution containing 5 ml. of saponin andapplying this solution to aclear film support such that the dry coatingthickness was 4 to 5 microns. These clear gelatin layers were processedthrough the solutions normally employed in color print work.

Sections 1 x /2" were cut from the clear film and superposed on theunexposed color print paper which had been processed in the normalmanner. These absorber hours in the Atlas Fade-Ometer and subjected tothe ultraviolet radiation as heretofore explained. The yellowdiscoloration resulting from ultraviolet degradation of unused colorformer was again determined by reflection density measurements. Inaddition the loss in yellow dye covered strips were then exposed for tenhours in an Atlas 5 density was determined by similar yellow dye densityFade-Ometer to the radiation of a single enclosed violet measurementswith correction made for the yellow stain carbon arc in which 20.3% ofthe emitted radiation is in developed. Results are tabulated below.

TABLE II Yellow UV absorber Stain. dye concentration, percent density,Ex. Ultraviolet absorber mgmJitJ incr. pereentloss 8 2%2-hy1roxy-5'-t-octylphenyl)naphtho- 27.5 67 18 Halo 6. 92-(2'-hydroxy-3',5-ditertiaryamylphenyl) 27.5 50 7.5

naphthotriazole. l 2-gZf-hydwxy-fi t-oetylphenyl)naphtho- 54 33 9.6

U820 9. 11 2-(2-hydroxy-3',5-ditertiaryamylphenyl) 27. 100 20. 7

benzotriazole. 2,2-dihydroxy-'octoxybenxophenone.. 27.5 100 11.4 13....do.. 54 83 7.4 14 Blank... 260 51. 0

the ultraviolet range. For comparison purposes both a blank sample andsamples covered with gelatin layers containing ultraviolet absorbers ofthe prior art were also prepared and exposed.

After this exposure the samples were placed in a densitometer todetermine the degree of yellow stain discoloration by reflection densitymeasurements. This discoloration is a result of degradation, by theincident ultraviolet radiation, of the unused color formers remaining inthe paper after processing. Results are tabulated below.

For Example 9, the sample containing the preferred compound of thisinvention [2-(2'-hydroxy-3',5-ditertiaryamylphenyl)naphthotriazole],there is a twofold decrease in the amount of yellow stain developed onexposure to ultraviolet radiation in comparison with those samplescontaining the absorber compounds of the prior art (Examples 11 and 12).At the same time the loss in yellow dye density in the aforesaid Example9 is 1.5 to 2.7 times less than the corresponding loss in the samplescompounded with the absorbers of the prior art. Since these EXAMPLES 8-14 These examples illustrate the suitability of the ultraviolet absorbercompounds of this invention when incorporated into one of the colorforming layers of a multilayer color photographic element.

Dispersions containing the ultraviolet absorber compound with a cyancolor former were prepared following a procedure analogous to thatdescribed in Examples 1-7 above with both the ultraviolet absorber andthe cyan color former dissolved in the solvents. The dispersioncomposition was constituted as listed below.

Ultraviolet absorber grams 6.0 Cyan color former [2,4 dichloro 3 methyl-6(2,4' ditertiaryamyl phenoxyacetamido)phenol] grams 6.0Dibutylphthalate ml 6.0 Butylbenzylphthalate ml 6.0 Gelatin -gr m 6.0Water ml 60.0

10% Alkanol B (propylated naphthalene sulfonate) ml. 10.0

Each dispersion was, in turn, admixed with red sensitized silver halideemulsions containing the necessary coating finals and this mixture wasthen coated over the yellow and magenta dye-forming layers on a papersupport to form a multilayer color photographic element. After theelement was given red, green and blue separation exposure and processed,it was then positioned for 10 results are measures of the intra-layerand extra-layer ultraviolet degradation effects respectively, they areindicative of the protective ability of the naphthotriazoles when eitherintimately admixed in the emulsion layer or applied as an exteriorcoating over the emulsion layer.

While exemplary embodiments of the invention have been described, thetrue scope of the invention is to be determined from the followingclaims.

We claim:

1. A photographic element comprising a support having thereon at leastone photographic silver halide emulsion layer and a superposed gelatinlayer, at least one of said layers containing a hydrophobic compoundhaving the formula:

wherein R, R and R each represents a member selected from the classconsisting of hydrogen, halogen, alkyl groups having from 1 to 20 carbonatoms, hydroxyalkyl, haloalkyl, cyanoalkyl, alkoxyalkyl, alkoxy,aryloxy, cyano, carbalkoxy, alkyl sulfonyl, sulfamyl, N-alkyl sulfamyl,N-phenyl sulfamyl, N-heterocyclic sulfamyLcarbamyl, N-alkyl carbamyl, Nphenyl carbamyl, N heterocyclic canbamyl and lactam methylene groups, atleast one of the groups R, R and R containing at least 3. carbon atoms.v

2. A photographic element as defined in claim 1 wherein at least one ofsaid photographic silver halide emulsion layers contains said compound.

3. A photographic element as defined in claim 2 wherein the layercontaining said compound is formed from a dispersion comprising ahydrophilic colloid binder material, a high-boiling, water immiscibleorganic plasticizer and said compound. v i I 4. A photographic elementas defined in claim 1 wherein said superposed gelatin layer containssaid compound;

5. A photographic element as definedin claim 4 wherein the superposedgelatin layer containing said compound, is formed from a dispersioncomprising gelatin, a high boiling water immiscible organic plasticizerand said compound.

6. A photographic element according to claim 1 in References CitedUNITED STATES PATENTS 3,004,896 10/ 1961 Heller et a1. 252-300 3,253,9215/1966 Sawdey 252-300 FOREIGN PATENTS 1,497,191 8/1967 France 96-84RONALD H. SMITH, Primary Examiner US. Cl. X.R.

